Water-insoluble monoazo dyestuffs containing a quinoline coupling component

ABSTRACT

WHEREIN A AS A RADICAL OF A DIAZO COMPONENT REPRESENTS DICHLORO-PHENYLENE, DINITRO-PHENYLENE, CYANO-NITRO-PHENYLENE, CHLORO-NITRO-PHENYLENE, NITRO-TRIFLUOROMETHYL-PHENYLENE, CHLORO-DINITRO-PHENYLENE, BROMO-DINITRO-PHENYLENE, CHLORO-NITRO-CYANO-PHENYLENE, BROMO-NITRO-CARBOMETHOXYPHENYLENE, BROMO-CYANO-PHENYLENE, METHYLSULFONYL-NITROPHENYLENE, DINITRO-TRIFLUOROMETHYL-PHENYLENE OR DINITROCARBONETHOXY-PHENYLENE, B REPRESENTS HYDROGEN OR LOWER ALKYL, AND C REPRESENTS HYDROGEN, PHENYL, LOWER ALKYLPHENYLENE, CHLORO-PHENYLENE, BENZYL, CYCLOHEXYL, HYDROXYETHYL, CYANOETHYL, HYDROXPROPYL OR N-BUTAN-3-ONYL, SAID DYESTUFF BEING SULTABLE FOR THE DYEING OR PRINTING OF CELLULOSE ACETATE OR SYNTHITIC POLYAMIDE OR POLYESTER FIBRES, THE DYEINGS OR PRINTS BEING DISTINGUISHED BY VERY GOOD FASTNESS PROPERTIES TO THERMOFIXATION, WASHING, RUBBING, WASTE GAS AND LIGHT.   5-(A-N=N-),8-(B-N(-C)-)QUINOLINE   A WATER-INSOLUBLE MONOAZO DYESTUFF OF THE FORMULA

United States Patent 3,637,647 WATER-INSOLUBLE MONOAZO DYESTUFFSCONTAINING A QUINOLENE COUPLING COMPONENT Konrad Opitz, Frankfurt amMain, Germany, assignor to 5 Farbwerke Hoechst Aktiengesellschaftvormals Meister Lucius & Bruning, Frankfurt am Main, Germany No Drawing.Filed June 3, 1970, Ser'. No. 43,187 Claims priority, applicationGermany, Jun 11, 1969, P 19 29 573.9 Int. Cl. C09b 29/36; D06p N02 US.Cl. 260-155 8 Claims ABSTRACT OF THE DISCLOSURE A water-insolublemonoazo dyestufi of the formula The present invention relates to newwater-insoluble 4O monoazo dyestuffs of the general Formula 1 in which Arepresents a radical of a diazo component of the benzene or naphthaleneseries which may be substituted by halogen atoms and/or alkyl, alkoxy,perfluoroalkyl, alkyl-sulfonyl, aryl-sulfonyl, carbalkoxy, carbonamido,cyano or nitro groups, for example chlorine or bromine atoms or methyl,ethyl, methoxy, ethoxy, trifluoromethyl, methylsulfonyl,phenyl-sult'onyl, carbomethoxy or carbo-ethoxy groups, B stands for ahydrogen atom or an alkyl radical, which may be substituted by halogenatoms and/ or hydroxy, cyano, alkoxy, acyl, acyloxy or carbalkoxygroups, C is a hydrogen atom or a lower alkyl radical, a cyclo-alkyl,aralkyl or aryl radical being free from carboxylic or sulfonic acidgroups, but which may be substituted by halogen atoms and/or hydroxy,cyano, alkoxy, acyl, acyloxy or carbalkoxy groups, and D and B, beingfree from carboxylic or sulfonic acid groups, may be substituted byhalogen atoms and/ or hydroxy, alkyl, alkoxy or acylamino groups. Thepresent invention relates further to a process for the manufacture ofthese water-insoluble monoazo dyestufi's, which comprises diazotizingamines of the general Formula 2 in which A is as defined above, andcombining them with coupling components of the general Formula 3 inwhich B, C D and E are as defined above.

For preparing the new dyestuffs there are used as diazo components ofthe general formula ANH advantageously aniline derivatives being freefrom water-solubilizi ng groups such as carboxylic or sulfonic acidgroups. Suitable examples are:

2,4-dinitro-aniline, 2-cyano-4-nitro-aniline, 2-chloro-4-nitroaniline,2-cyano-4-nitro-6-chloro-aniline, 2-cyano-4-nitro-6-bromo-aniline,2-carbomethoxy-4-nitro-6-bromo-aniline, 2,4-dinitro6-chloro-aniline,2,4-dinitro-6-bromo-aniline,

2,5 -dichloro-aniline, 2-methyl-sulfonyl-4-nitro-aniline,2-trifluoromethyl-4-nitro-aniline,2,4-dinitro-6-trifiuoro-methyl-aniline,2,4-dinitro-6-carbomethoxy-aniline.

Diazotation of these aniline derivatives is carried out according tosuitable known processes.

Examples of the coupling components of the aforementioned generalFormula 3, used in the process of the invention and prepared accordingto known methods, are

S-phenylamino-quinoline,

8- (4'-methylphenylamino) -quinoline,

8- (4-chlorophenylamino)-quinoline, 8-fl-cyano-ethylamino-quinoline,8-B-hydroxy-ethylamino-quinoline,8-N-ethyl-N-fi-cyano-ethylamino-quinoline, 8-cyclohexylamino-quinoline,S-benzylamino-quinoline, and 8-n-butane-3-onylamino-quinoline.

The coupling reaction is advantageously carried out in an aqueousmedium, and it may be advantageous to eliminate the acid excessresulting from the diazotation by adding acid-binding agents, such assodium acetate, sodium hydrogen carbonate, sodium or potassium carbonateor sodium hydroxide solution. The dyestuffs so obtained arewater-insoluble and separate in the form of crystals. They may beisolated for example by filtration. The dyestuffs are thenadvantageously washed with water to eliminate electrolytes.

By using preparations containing the new dyestuifs in a finely dividedform as well as a dispersing agent, there are obtained on syntheticfibres, such as cellulose-acetate and polyamide fibres, especially onpolyester fibres, for example polyethyleneglycol-terephthalate fibres,prints and dyeings of high colour intensity and a very good build-up,which have excellent fastness properties to processing and to use. Theyexcel especially by their very good fastnesses to thermofixation,washing, waste gas, rubbing and light.

For the dyeing of polyester fibres, the new dyestuffs are advantageouslyused as a granulate or a powder or as a liquid preparation ready forpouring. They are suited for dyeings from aqueous baths at temperatureshigher than C. under pressure or at about 100 C. in the presence ofcarriers, as well as for the Thermosol process, in which polyester fibrewoven or knitted fabrics are padded .with suspensions of the newdyestuffs, dried at temperatures below 100 C. and exposed for a shorttime to temperatures of from about 180 to 280 C. The new dyestuffs arevery well suited further for the dyeing of fibre mixtures containingpolyester fibres. When, for example, polyester/wool mixtures are dyed,the wool portion is only superficially dyed, so that this dyeing can beeasily removed by a reduction after-treatment or a washing with anemulsifier.

Further, the new dyestuffs are highly appropriate also for the dyeing ofpolyester fibres from organic solvents; halogenated hydrocarbons havinga boiling range of from 100 to 180 C., preferably of from 110 to 150 C.,for example perchloroethylene, are especially suitable in this case.From solutions of the new dyestuffs in perchloroethylene, dyeings areobtained on polyester fibres at boiling temperatures which excel bytheir high colour intensity and by the same fastnesses to processing andto use as obtained with usual dyeing methods.

For printing polyester fibre material, the new dyestuffs are applied inthe form of water containing preparations which contain, besides thefinely divided dyestuff, suitable thickeners, for example carbomethoxycellulose or locust bean flour preparations or mixtures of thesesubstances, and fixation accelerators. Fixation is carried out bysteaming for 30 to 60 minutes under atmospheric pressure or by steamingfor 10 to 30 minutes under increased pressure up to 2 atmospheres gauge.Fixation may also be carried out by the action of hot air at atemperature of from 180 to 220 C. during 30 to 90 seconds.

The following examples illustrate the invention. Parts and percentagesare by weight unless otherwise stated, the relation of parts by weightto parts by volume being the same as of a kilogram to a litre.

EXAMPLE 1 163 parts of 2-cyano-4-nitro-aniline are stirred with 750parts of glacial acetic acid, partly dissolved and then, while cooling,diazotized at room temperature with 324 parts of 40%-nitrosyl-sulfuricacid, which are slowly added dropwise. A clear solution is resultingwhich is stirred for another hour at room temperature. This diazosolution is fed, while stirring, into a solution of 220 parts ofS-phenylamino-quinoline in 250 parts of glacial acetic acid, 200 partsby volume of 5 N hydrochloric acid and 1000 parts of water, whichcontains further 1000 parts of ice. While the diazo solution is fed in,further 2000 parts of ice are added in portions.

Subsequently, the pH of the solution is adjusted to 4 by adding 650parts of sodium acetate. The coupling process is completed after a shorttime. The dyestulf precipitated in the form of crystals issuction-filtered and the filter cake is washed with Water until it isfree from electrolytes. After the drying at 60 C., 376 parts of adyestulf of the formula EN Q are obtained which, in a finely dividedform, on polyester fibres yields clear and intense violet dyeings havingvery good fastnesses to light and to thermofixation.

EXAMPLE 2 217.5 parts of 2,4-dinitro-6-chloro-aniline are introducedinto 740 parts of concentrated sulfuric acid and slowly combined at roomtemperature, while stirring and cooling, with 324 parts of40%-nitrosyl-sulfuric acid. A clear solution results which is stirredfor another hour at room temperature. The diazo solution so obtained isfed, while thoroughly stirring, into a solution of 234 parts of 8-(4-methylphenylamino)-quinoline in 400 parts by volume of 5 N hydrochloricacid and 500 parts of water, which further contains 3000 parts of ice.Coupling is complete after a short time. The reaction mixture is stirredfor 4 another 2 hours and the dyestuff precipitated in the form ofcrystals is isolated by suction-filtration and washing with water untilthe filter cake is free from electrolytes. After the drying at C., 435parts of a dyestuff of the 1110, are obtained. This dyestuff, in afinely divided form yields on polyester fibres clear blue dyeings havingvery good fastnesses to light and to thermofixation.

EXAMPLE 3 262 parts of 2,4-dinitro-6-bromo-aniline are introduced into740 parts of concentrated sulfuric acid and slowly combined at roomtemperature, while stirring and cooling, with 324 parts of40%-nitrosyl-sulfuric acid. A clear solution results which is stirredfor another hour at room temperature. The diazo solution so obtained isfed, while thoroughly stirring, into a solution of 220 parts of 8-N-phenylamino-quinoline in 400 parts by volume of 5 N hydrochloric acidand 500 parts of Water, which further contains 3000 parts of ice.Coupling is completed after a short time. The reaction mixture isstirred for another 2 hours and the dyestuff precipitated in the form ofcrystals is isolated by suction-filtration and Washing with water untilthe filter cake is free from electrolytes. After the drying at 60 C.,465 parts of a dyestuff of the formula are obtained which, in a finelydivided form, yields on polyester fibres reddish navy-blue dyeingshaving very good fastnesses to light and to thermofixation.

EXAMPLE 4 217.5 parts of 2,4-dinitro-6-chloro-aniline are introducedinto 740 parts of concentrated sulfuric acid and slowly combined at roomtemperature, while stirring and cooling, with 324 parts of40%-nitrosyl-sulfuric acid. A clear solution results which is stirredfor another hour at room temperature. The diazo solution so obtained isfed, while thoroughly stirring, into a solution of 226 parts of8-(cyclo-hexylamino)-quinoline in 400 parts by volume of 5 Nhydrochloric acid and 500 parts of water, which further contains 3000parts of ice. Coupling is completed after a short time. The reactionmixture is stirred for another 2 hours and the dyestuff precipitated inthe form of crystals is isolated by suction-filtration and washing withwater until the filter cake is free from electrolytes. 410 parts of adyestuff of the formula are obtained which, in a finely divided form,yields on polyester fibres intense navy-blue dyeings of very goodfastnesses to light and to thermofixation.

EXAMPLE 5 163 parts of 2-cyano-4-nitraniline are stirred with 750 partsof glacial acetic acid, partly dissolved and then diazotized at roomtemperature, while cooling, with 324 parts of 40%-nitrosyl-sulfuricacid, which are slowly added dropwise. A clear solution results which isstirred for another hour at room temperature. This diazo solution isfed,

6 while stirring, into a solution of 197 parts of 8-B-cyanoprints havingvery good fastnesses to therrnofixation, to ethylamino-quinoline in 250parts of glacial acetic acid, washing, rubbing and to light areobtained. 200 parts by volume of N hydrochloric acid and 1000 EXAMPLE 41parts of water, which contains further 1000 parts of ice. t While thediazo solution is fed in, further 2000 parts of 5 When uslng 1n Example3 instead of 262 parts of 2,4-

ice in portions are added. dinitro 6 bromo aniline 217.5 parts of 2,4dinitro-6- Subsequently, the pH of the solution is adjusted to 4chloro-aniline and proceeding for the rest as described in by adding 650parts of sodium acetate. Coupling is com- Example 3, 420 Parts Of thedyest if 0f the f mula plete after a short time. The dyestufl?precipitated in the form of crystals is suction-filtered and the filtercake is washed with water until it is free from electrolytes. After thedrying at 60 C. 342 parts of a dyestutf of the formula 02N- N= ON N 1102 of Example 7 are obtained which, from a solution in OQNperchloroethylene at boiling temperature, yields on polyester fibresintense blue dyeings having very good fastnesses to thermofixation andto light.

We claim: 1. A water-insoluble monoazo dyestufi of the formula areobtained which, in a finely divided form, yields on polyester fibresviolet dyeings having excellent fastnesses to light and tothermofixation.

When the diazo components listed in column 1 of the following table arediazotized according to one of the methods described in theaforementioned examples or B another suitable method, and when they arecoupled, optionally while eliminating the acid excess resulting from thediazotation by adding an acid-binding agent, with the C couPling'compoflentjs listed in f l then dyestuffs wherein A as a radical of adiazo component represents are obtained which, in a finely drvlded form,on poly dichloro-phenylene, dinitro-phenylene, cyano-nitro-phenfibres yf dyelngs havlng the Shades glvfll 111 column 3 ylene,chloro-nitro-phenylene, nitro-trifiuoromethyl-phenand having generallythe same good fastnesses as in the ylene, chloro-dinitro-phenylene,bromo-dinitro-phenylene, examples cited. chloro nitro cyano phenylene,bromo nitro-carborne- TABLE Example Shade on polyester No. Diazocomponent Coupling component fibres 6 2,4-dinitro-aniline- 7..-2,4-dinitro-6-chloroanillne 2-cyano-4-nltro-6 oh1oro-aniline Reddishviolet. Reddish navy blue. Navy blue.

8-ph5nylamino-quinoline.

9... 2-carbomethoxy-4-nitro-6-bromo-aniline.. Violet. 10.-2chloro-4-nitro-anlline Do. 11.-. 2,4-dinltro-aniline Blulsh violet.12... 2-eyano-4nitro-aniline Reddish blue. 13...2,4-dinltro-6-bromoanlline Blue. 14... 2,5-dichloro-anlline Red. 152,4-dinltro6-chloro-aniline 8-benzylamino-quinoline.... Bluish violet.16 2,4-dinltr0aniline S-cyclohexylamino-quinoline. Violet. 172-oyano-4-nitro-aniline Do. 18 2,4-dinltro-6bromo-aniline. Navy blue 192,4-dinitro-6-chloro-anlline iolet. 20 ..do Reddlsh blue. 212-cyano-4-nitro-an Reddish violet. 22... 2,4dinitro-6-chloro-a Reddishblue. 23... 2,4-dinltro-6-bromo-aniliue. Do. 24...2-cyano-4-nltro-aniline Violet. 25... 2-nitro4trifiuoro-methyl-anilineRed-brown, 26... 2-trliluoro-methyl-i nitro aniline Blulsh red. 27.--2,4 dinitro-anillne Reddish violet. 28.-. Zcyano-Qnitro-aniline Do.29--. 2,4'dinitro-6-chloro-aniline.. Reddish blue. 30..-2,4-dinltro'aniline Bluish red. 31... 2,4dlnltro-6-bromo-aniline. Bluishviolet. 32 do .do Do. 33 2,4-dinitro-6-chloro-anillne...Sfi-hydroxy-ethylamino-quiuoline Navy blue. .34 2,4-dinltro-aniline8w-hydroxypropylamino-quinoline Reddish violet. 352-cyano-4-nitro-aniline do Violet. 36 2,4-dinitro-6-chloro-anil Reddlshblue. 37 2-cyano4-nitro-anilina. Reddish violet. 38..-2,4-dinitro6-chloroanil' o Bluish violet. 39 2cyano-4-nitro-anlline--...8- 8-phenyethylamino-qulnoline Violet.

EXAMPLE 40 thoxy phenylene, bromo cyano phenylene, methylsulfonylnitro-phenylene dinitro-trifluoromethyl-phenylene h d s if of he formulaT e ye t or drnrtro-carbomethoxy-phenylene, B represents hydrogen orlower alkyl, and C represents hydrogen, phenyl, I lower alkyl-phenylene,chloro-phenylene, benzyl, cyclo- O N NH hexyl, hydroxyethyl, cyanoethyl,hydroxypropyl or n- 2 butan-3-onyl.

l 2. The water insoluble monoazo dyestuff of the 2 formula obtainedaccording to the method described in Example 3 is applied in a watercontaining preparation which contains, besides the finely divideddyestuff, a dispersing agent, a thickener such as carboxymethylcellulose and a fixation accelerator, according to usual processes forthe printing of polyester fibre materials. Intense navy-blue 8 3. Thewater-insoluble monoazo dyestuff of the 7. The water-insoluble monoazodyestufi of the formula formula.

Cl \N 0,N -N=N NHCH I CN 4. The water-insoluble monoazo dyestufl? of theN02 formula 10 8. The water-insoluble monoazo dyestufi of the Cl \1formula P l N N0, 5. The water-insoluble monoazo dyestuif of the ONformula N N0, N

| References Clted @NH FOREIGN PATENTS 1|? 800,144 8/1958 Great Britain260-155 6. The water-insoluble monoazo dyestuff of the CHARLES PARKER, my m ner formula D. M. PAPUGA, Assistant Examiner

